The carbonylation of methanol produces acetic acid:CH3OH+CO→CH3COOHPrior to 1970, acetic acid was made using cobalt catalysts. A rhodium carbonyl iodide catalyst was developed in 1970 by Monsanto. The rhodium catalyst is considerably more active than the cobalt catalyst, which allows lower reaction pressure and temperature. Most importantly, the rhodium catalyst gives high selectivity to acetic acid.
One problem with the original Monsanto process is that a large amount of water (about 14%) is needed to produce hydrogen in the reactor via the water-gas shift reaction (CO+H2OCO2+H2). Water and hydrogen are needed to react with precipitated Rh(III) and inactive [RhI4(CO)2]− to regenerate the active Rh(I) catalyst. The large amount of water increases the amount of hydrogen iodide, which is highly corrosive and leads to engineering problems. Further, removing a large amount of water from the acetic acid product is costly.
In the late '70s, Celanese modified the Monsanto process by adding lithium iodide salt to the carbonylation. Lithium iodide salt increases the catalyst stability by minimizing the side reactions that produce inactive Rh(III) species and therefore the amount of water needed is reduced. However, the high concentration of lithium iodide salt promotes stress crack corrosion of the reactor vessels. Furthermore, the use of iodide salts increases the iodide impurities in the acetic acid product.
In the late '90s, Lyondell Chemical Company (by its predecessors) developed a new rhodium carbonylation catalyst system that does not use iodide salt. The catalyst system uses a pentavalent Group VA oxide such as triphenyiphosphine oxide as a catalyst stabilizer. The Lyondell catalyst system not only reduces the amount of water needed but also increases the carbonylation rate and acetic acid yield. See U.S. Pat. No. 5,817,869.
One challenge still facing the industry is that lowering water concentration in the methanol carbonylation results in increased aldehyde formation. Methods for reducing aldehyde concentration in acetic acid are known. For instance, U.S. Pat. No. 6,667,418 discloses a method for reducing aldehydes by oxidizing them with air, hydrogen peroxide, and other free radical initiators in an integrated acetic acid production process at an elevated temperature. Introducing free radical initiators into acetic acid production process is inconvenient because free radical initiators are explosive. U.S. Pat. No. 7,524,988 discloses a method which comprises reacting an acetic acid stream containing aldehyde impurities with glycols to form corresponding dioxanes. The dioxanes are subsequently removed from the acetic acid by, e.g., distillation. However, the dioxanes are stable and the glycols thus cannot be easily recovered.
New methods for reducing aldehydes in acetic acid are needed. Ideally, the aldehyde can be effectively removed by forming a product which can be readily decomposed to recover the starting materials.